Silane coupling agent and glass fiber product for laminates

ABSTRACT

A glass fiber product for laminates is provided having excellent epoxy resin impregnation properties and solvent resistance, high soldering heat resistance, good heat shock resistance and low water adsorption properties, and to a silane coupling agent for providing such a glass fiber product. 
     The silane coupling agent is prepared by reacting 2.3 to 4.0 mols of a haloalkylalkoxysilane with 1 mol of a diamine having N atoms to which 4 active hydrogen atoms are bound, a silane coupling agent prepared by reacting 1.3 to 3.0 mols of a haloalkylalkoxysilane with 1 mol of a diamine having N atoms to which 3 active hydrogen atoms are bound and to which one alkylsilyl group is bound, or a silane coupling agent prepared by reacting 0.3 to 2.0 mols of a haloalkylalkoxysilane with 1 mol of a diamine having N atoms to which 2 active hydrogen atoms are bound and to which 2 alkylsilyl groups are bound. A silane coupling agent prepared by reacting the diamine with a haloalkylalkoxysilane and a halomethylstyrene is also provided as is a glass fiber product for laminates treated with the above-mentioned silane coupling agent.

BACKGROUND OF THE INVENTION

(1) Field of the Invention

The present invention relates to a novel silane coupling agent and aglass fiber product for laminates treated with the silane couplingagent.

(2) Description of the Prior Art

In general, a silane coupling agent has the structure in which a siliconatom simultaneously has an alkoxy group capable of reacting with thesurface of an inorganic material and an organic functional group whichis reactive or compatible with an organic material, and therefore thesilane coupling agent is used as an adhesion improver between theorganic and inorganic materials.

For example, the silane coupling agents are widely utilized with theintention of improving mechanical strength, electrical characteristics,water resistance, heat resistance, adhesive properties and the like inthe fields of the surface treatment of glass fibers and variousinorganic fillers as well as the modification of reinforced plastics,sealants, adhesives and coating materials by adding the silane couplingagent itself to their matrix resins.

Above all, the application of the silane coupling agent to the surfacetreatment of glass fibers for glass epoxy laminates and the like is oneof the applications in which some effects of the silane coupling agentcan be most effective.

Examples of conventional surface treating agents suitable for glassfibers, particularly glass fibers for glass epoxy laminates includesilane compounds such as 3-aminopropyltriethoxysilane,3-glycidoxypropyltrimethoxysilane and3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxysilanehydrochloride.

In recent years, technical innovation made rapid progress in the fieldof glass fibers, particularly glass epoxy laminates, and needless tosay, these laminates are required to be excellent in epoxy resinimpregnation, properties and solvent resistance. Particularly, with theadvance of soldering techniques in printed-circuit board-manufacturingprocesses and manufacturing techniques in multi-layer printed-circuitboard-manufacturing processes when glass epoxy laminates are used asprinted circuit boards, it is demanded that they have higher heatresistance and lower water absorption properties.

In these days, however, the conventional silane coupling agents scarcelysatisfy these requirements, and another silane coupling agent havingmore excellent functions is desired.

On the other hand, most of the silane coupling agents presently used arehigh-boiling single compounds manufactured by isolation andpurification.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a glass fiber productfor laminates having excellent epoxy resin impregnation properties andsolvent resistance, high soldering heat resistance, good heat shockresistance and low water absorption properties.

Another object of the present case is to provide a silane coupling agentused to manufacture such a glass fiber product.

Inventors of the present application have intensively conducted researchto solve the above-mentioned problems, and as a result, they have foundthat an aminosilane compound formed by subjecting a diamine compound anda haloalkylalkoxysilane, which are raw materials, to a condensationreaction in a limited ratio or another aminosilane compound formed bythe addition reaction of halomethylstyrene to the condensation reactionproduct can be directly used in the form of various mixtures withoutundergoing any particular operations of isolation and purification, andthat the employment of the above-mentioned aminosilane compound cansolve these problems. The present invention has been achieved on thebasis of this knowledge.

That is, the present invention is directed to

(1) a silane coupling agent prepared by reacting 2.3 to 4.0 mols of ahaloalkylalkoxysilane with 1 mol of a diamine having N atoms to which 4active hydrogen atoms are bound (hereinafter referred to as "diamineA"),

(2) a silane coupling agent prepared by reacting 1.3 to 3.0 mols of ahaloalkylalkoxysilane with 1 mol of a diamine having N atoms to one ofwhich one alkylsilyl group is bound and to the residual bonds of which 3active hydrogen atoms are bound (hereinafter referred to as "diamineB").

(3) a silane coupling agent prepared by reacting 0.3 to 2.0 mols of ahaloalkylalkoxysilane with 1 mol of a diamine having N atoms to each oreither of which 2 alkylsilyl group are bound and to each or either ofwhich 2 active hydrogen atoms are bound (hereinafter referred to as"diamine C"),

(4) a silane coupling agent prepared by reacting a halomethylstyrenewith a reaction product obtained by reacting 1 mol of the abovementioned diamine A with 2.3 to 3.5 mols of a haloalkylalkoxysilane, areaction product obtained by reacting 1 mol of the above mentioneddiamine B with 1.3 to 2.5 mols of a haloalkylalkoxysilane, or a reactionproduct obtained by reacting 1 mol of the above mentioned diamine C with0.3 to 1.5 mols of a haloalkylalkoxysilane, the amount of the aforesaidhalomethylstyrene being not more than 80 mol% of mol amounts obtained bysubtracting the mols of the used haloalkylalkoxysilane from the mols ofthe active hydrogen of the used diamine,

(5) a process for preparing a silane coupling agent described in any oneof the previous paragraphs (1) to (4) which comprises the step ofreacting a haloalkylalkoxysilane with a diamine having at least an Natom to which an active hydrogen atom is bound or active hydrogen atomsare bound, while a secondarily produced hydrogen halide is removed bythe use of a basic substance which is inert to the raw materials and thereaction product.

(6) a glass fiber product for laminates treated with the silane couplingagent described in any one of the previous paragraphs (1) to (4).

DETAILED DESCRIPTION OF THE INVENTION

A haloalkylalkoxysilane which can be used in the practice of the presentinvention is preferably a compound represented by the formula ##STR1##wherein each of R¹ and R² is independently a substituted orunsubstituted alkyl group, an aryl group or an alkenyl group, each ofsaid groups having 1 to 6 carbon atoms, R³ is a straight-chain orbranched alkylene group having 1 to 6 carbon atoms, n is 1, 2 or 3, andX is a halogen atom.

Examples of such a haloalkylalkoxysilane compound include3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane,3-bromopropyltrimethoxysilane, 3-bromopropyltriethoxysilane,4-chlorobutyltrimethoxysilane, 4-chlorobutyltriethoxysilane,3-chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane,3-bromopropylmethyldimethoxysilane, 3-bromopropylmethyldiethoxysilane,3-chloropropyldimethylmethoxysilane, 3-chloropropyldimethylethoxysilane,3-bromopropyldimethylmethoxysilane and3-bromopropyldimethylethoxysilane.

Examples of the diamine A used in the present invention include primaryor secondary ethylenediamine, diaminopropane, diaminobutane,hexamethylenediamine, phenylenediamine, xylylenediamine,diaminobiphenyl, diaminodiphenylmethane and naphthylenediamine.

Examples of the diamine B mentioned above includeN-2-aminoethylaminopropylmethyldimethoxysilane,N-2-aminoethylaminopropylmethyldiethoxysilane,N-2-aminoethylaminopropyltrimethoxysilane,N-2-aminoethylaminopropyltriethoxysilane,N-2-aminoethylaminopropyldimethylmethoxysilane,N-2-aminoethylaminopropyldimethylethoxysilane,N-trimethoxysilylpropyldiaminopropane,N-trimethoxysilylpropyldiaminohexane,N-trimethoxysilylpropylphenylenediamine,N-trimethoxysilylpropyldiaminobiphenyl,N-trimethoxysilylpropyldiaminodiphenylmethane and(aminoethylaminomethyl)phenethyltrimethoxysilane.

Examples of the diamine C incudeN,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine,N,N-bis[3-(trimethoxysilyl)propyl]ethylenediamine,N,N'-bis[3-(methyldimethoxysilyl)propyl]ethylenediamineN,N-bis[3-(methyldimethoxysilyl)propyl]ethylenediamine,N,N'-bis[3-(dimethylmethoxysilyl)propyl]ethylenediamine,N,N-bis[3-(dimethylmethoxysilyl)propyl]ethylenediamine,N-[3-(methyldimethoxysilyl)propyl]-N'-[3-(trimethoxysilyl)propyl]ethylenediamine,N-[3-(methyldimethoxysilyl)propyl]-N-[3-(trimethoxysilyl)propyl]ethylenediamine,N,N'-bis[3-(trimethoxysilyl)propyl]diaminopropane,N,N'-bis[3-(trimethoxysilyl)propyl]diaminohexane,N,N'-bis[3-(trimethoxysilyl)propyl]phenylenediamine,N,N'-bis[3-(trimethoxysilyl)propyl]diaminobiphenyl andN,N'-bis[3-(trimethoxysilyl)propyl]diaminodiphenylmethane.

Examples of the halomethylstyrene used in the present invention includechloromethylstyrene, bromomethylstyrene and iodomethylstyrene, butpractically methylstyrene chloride is convenient.

The reaction is carried out in a dried organic solvent which is inert tothe raw materials.

Examples of the solvent include lower alcohols such as methanol andethanol, ethers such as tetrahydrofuran and dioxane, and aromatichydrocarbons such as toluene and xylene. These solvents are preferahlyused in a dry state. If a large amount of moisture is contained in thesolvent, the alkoxy group of the raw materials and product undergoeshydrolysis in order to form a condensate, with the result that the yieldof the desired product deteriorates.

The reaction between the haloalkylalkoxysilane and the diamine A, B or Cproceeds on the basis of dehydrodiamine halogenation reaction between anN-H group of the amine and a C-X group (X is a halogen atom) of thehaloalkylalkoxysilane.

In order to obtain the excellent coupling agent, it is important thatthe reaction proceed sufficiently so that the conversion of the rawmaterials may be 100%. However, the diamine, A, B or C, which is the rawmaterial captures the released hydrogen halide, so that the reactivityof the diamine declines, which impedes the smooth progress of thereaction. In addition, an intermediate in the reaction and the reactionproduct also capture the hydrogen halide of the by-product. Inconsequence, when this reaction product is further reacted with thehalomethylstyrene, the hydrogen halide which reacts with to the reactionproduct impedes the reaction with the halomethylstyrene.

Thus, it is necessary to remove the hydrogen halide from the diamine,the intermediate and the reaction product with which it reacts, by abasic material inert to the diamine of the raw material, theintermediate and the reaction product.

It is preferred that this basic material is inert to the raw materialdiamine, intermediate and reaction product and has a higher basicitythan the raw material diamine or the like.

Examples of the basic material include metallic alkoxides such as sodiummethylate and sodium ethylate, and organic bases such as triethylamine,triethylenediamine, 1,8-diazabicyclo(5,4,0)undecene-7.

In reacting the haloalkylalkoxysilane with the diamine A, thehaloalkylalkoxysilane is used in an amount of 2.3 to 4.0 mols,preferably 2.4 to 3.5 mols per mol of the diamine A. If the amount ofthe haloalkylalkoxysilane is less than 2.3 mols, a large amount of theraw material diamine A remains in an unreacted state, and the amount ofcomponent which can function as the coupling agent decreases. Inaddition, it is also impossible to obtain any silane coupling agentwhich can provide the glass fiber product for laminates having excellentepoxy resin impregnation properties and solvent resistance, highsoldering heat resistance, good heat shock resistance and low waterabsorption properties.

In reacting the haloalkylalkoxysilane with the diamine B, thehaloalkylalkoxysilane is used in an amount of 1.3 to 3.0 mols,preferably 1.4 to 2.5 mols per mol of the diamine B. If the amount ofthe haloalkylalkoxysilane is less than 1.3 mols, it is impossible toobtain any silane coupling agent which can provide the glass fiberproduct for laminates having excellent epoxy resin impregnationproperties and the above-mentioned various characteristics.

In reacting the haloalkylalkoxysilane with the diamine C, thehaloalkylalkoxysilane is used in an amount of 0.3 to 2.0 mols,preferably 0.4 to 1.5 mols per mol of the diamine C. If the amount ofthe haloalkylalkoxysilane is less than 0.3 mols, it is impossible toobtain any silane coupling agent which can provide the glass fiberproduct for laminates having excellent epoxy resin impregnationproperties and the above-mentioned various characteristics.

When the haloalkylalkoxysilane is used in an amount more than the molesof the active hydrogen of the diamine, the unreactedhaloalkylalkoxysilane remains, which is inconveniently uneconomical andwhich lowers the concentration of the desired effective component. Inthis case, it can be presumed that the unreacted haloalkylalkoxysilaneis removed by distillation, or the like, but this means is alsoinconvenient, since a distillation step is required.

Consequently, in reacting the haloalkylalkoxysilane with the diamine A,B or C, it is preferred that the haloalkylalkoxysilane is used in anamount of 4.0, 3.0 or 2.0 mols, respectively, with respect to 1 mol ofthe diamine A, B or C.

The start of the reaction is made by dissolving thehaloalkylalkoxysilane and the diamine A, B or C in the above-mentionedsolvent, or adding dropwise the haloalkylalkoxysilane to the diamine A,B or C. This reaction proceeds at a temperature of 60° C. or more, butthe preferable range of the reaction temperature is from 100° to 180° C.

As the reaction proceeds, the secondarily produced hydrogen halidereacts with the raw materials and product. Therefore, as the reactionproceeds a reaction rate decreases gradually until the reaction attainsequilibrium.

At this point the basic material is added to the system in an amountcorresponding to that of the secondarily produced hydrogen halide inorder to remove the hydrogen halide from the raw materials and product,whereby the reaction rate can be recovered.

In this way, the steps of the reaction and the removal of the hydrogenhalide by the basic material are repeatedly carried out until theconversion of the raw materials has reached substantially 100%, andafterward the reaction is brought to an end.

Another novel silane coupling agent comprising a composition of variouscompounds is a silane coupling agent prepared by reacting ahalomethylstyrene with a reaction product obtained by reacting 1 mol ofthe diamine A with 2.3 to 3.5 mols of a haloalkylalkoxysilane, areaction product obtained by reacting 1 mol of the diamine B with 1.3 to2.5 mols of a haloalkylalkoxysilane, or a reaction product obtained byreacting 1 mol of the diamine C with 0.3 to 1.5 mols of ahaloalkylalkoxysilane, the amount of the aforesaid halomethylstyrenebeing not more than 80% of the mol amounts given by subtracting the molsof the haloalkylalkoxysilane used from the mols of the active hydrogenof the diamine used (the reaction product obtained by reacting thediamine A, B or C with the haloalkylalkoxysilane in such a ratio, whichis to be reacted with the halomethylstyrene, will be hereinafterreferred to as "reaction product F").

In reacting the haloalkylalkoxysilane with the diamine A, thehaloalkylalkoxysilane is used as a raw material in an amount of 2.3 to3.5 mols, preferably 2.4 to 3.5 mols per mol of the diamine A. If theamount of the haloalkylalkoxysilane is less than 2.3 mols, it is alsoimpossible to obtain any silane coupling agent which can provide theglass fiber product for laminates having excellent epoxy resinimpregnation properties and solvent resistance, high soldering heatresistance, good heat shock resistance and low water absorptionproperties. Inversely, if the amount of the haloalkylalkoxysilane ismore than 3.5 mols, the addition amount of the halomethylstyrene isdeficient at the time of the subsequent reaction with thehalomethylstyrene.

In reacting the haloalkylalkoxysilane with the diamine B, thehaloalkylalkoxysilane is used in an amount of 1.3 to 2.5 mols,preferably 1.4 to 2.5 mols per mol of the diamine B. If the amount ofthe haloalkylalkoxysilane is less than 1.3 mols, it is impossible toobtain any silane coupling agent which can provide the glass fiberproduct for laminates having excellent epoxy resin impregnationproperties and the above-mentioned various characteristics. Inversely,if the amount of the haloalkylalkoxysilane is more than 2.5 mols, theaddition amount of the halomethylstyrene is deficient at the time of thesubsequent reaction with the halomethylstyrene.

In reacting the haloalkylalkoxysilane with the diamine C, thehaloalkylalkoxysilane is used in an amount of 0.3 to 1.5 mols,preferably 0.4 to 1.5 mols per mol of the diamine C. If the amount ofthe haloalkylalkoxysilane is less than 0.3 mols, it is impossible toobtain any silane coupling agent which can provide the glass fiberproduct for laminates having excellent epoxy resin impregnationproperties and the above-mentioned various characteristics. Inversely,if the amount of the haloalkylalkoxysilane is more than 1.5 mols, theaddition amount of the halomethylstyrene is deficient at the time of thesubsequent reaction with the halomethylstyrene.

The start of the reaction is made by dissolving thehaloalkylalkoxysilane and the diamine A, B or C in the above-mentionedsolvent, or adding dropwise the haloalkylalkoxysilane to the diamine A,B or C. The reaction proceeds at a temperature of 60° C. or more, butthe preferable range of the reaction temperature is from 100° to 180° C.

As the reaction proceeds,, the secondarily produced hydrogen halidereacts with the raw materials and product. Therefore, time of thereaction proceeds, a reaction rate decreases gradually until thereaction attains equilibrium, as described above.

At this point a basic substance is added to the system in an amountcorresponding to that of the secondarily produced hydrogen halide inorder to remove the hydrogen halide from the raw materials and product,whereby the reaction rate can be recovered.

In this way, the two processes of the reaction and the removal of thehydrogen halide by the basic material are repeatedly carried out untilthe conversion of the raw materials has reached substantially 100%, andafterward the reaction is brought to an end. In consequence, the desiredreaction product F is obtained.

In the reaction between the reaction product F and thehalomethylstyrene, the amount of halomethylstyrene is preferably notmore than 80 mol% of the mol amounts given by subtracting mols of thehaloalkylalkoxysilane used from mols of the active hydrogen of thediamine used. If the amount of the halomethylstyrene is more than 80%the product manufactured therefrom is difficult to dissolve in waterwhen the product is used in the form of an aqueous solution. Inaddition, the use of too much of the halomethylstyrene is uneconomical.

The reaction is begun by dissolving the reaction product F in theabove-mentioned solvent and then adding dropwise the halomethylstyreneto the resulting solution. As the addition proceeds, the temperature ofthe reaction system rises gradually from exothermic heat produced. Thereaction is performed in the temperature range of from room temperatureto 100° C., preferably 30° to 80° C. for a period of 1 to 10 hours (theresulting reaction product will be hereinafter referred to as "reactionproduct G").

In the reaction product obtained by the reaction between thehaloalkylalkoxysilane and the diamine A, B or C, and in the reactionproducts F and G, many kinds of compounds are contained. The reactionproduct F or the reaction product obtained by the reaction between thehaloalkylalkoxysilane and the diamine A, B or C is considered to be acomposition of various molecules in which 0 to 4 alkoxysilylalkyl groupsare bound to 1 molecule of the diamine A, B or C. Furthermore, thereaction product G is considered to be a composition of variousmolecules in which 0 to 4 halomethylstyrenes are bound to 1 molecule ofdiamine contained in the reaction product F.

The constitutional ratio of the various products depends upon a blendratio of the raw materials and reaction conditions, and therefore it isnecessary to optimize the constitutional ratio for each application soas to obtain good performace.

Owing to this optimization, when used as a surface treating agent, thesilane coupling agent of the present invention can be adapted to changesin treatment conditions.

The silane coupling agent of the present invention is useful as thesurface treating agent for inorganic materials in common with usualsilane coupling agents. Examples of the inorganic material to which thesilane coupling agent of the present invention can be applied includenaturally occurring minerals and artificially synthesized minerals suchas glass, silica, alumina, talc, kaolin clay, mica, calcium carbonate,potassium titanate, silas, aluminum hydroxide, zeolite, titanium oxide,asbestos, silicon nitride and iron oxide. In addition, the silanecoupling agent of the present invention can also be applied to metalssuch as stainless steel, aluminum and copper which are oxidized andcovered with an oxide layer.

It has been found that a glass fiber product for printed circuit boardshaving excellent epoxy resin impregnation properties and solventresistance, high soldering heat resistance, good heat shock resistanceand low water absorption properties can be obtained by treating theglass fiber product itself with the silane coupling agent described inany one of the previous paragraph (1) to (4).

The amount of the silane coupling agent used for this treatment dependsupon the kind of glass fiber product, but it is from 0.2 to 3.0% (% byweight; the same shall apply hereinafter), preferably 0.5 to 2.0% interms of the concentration of a treating solution, and in other words,the amount of the silane coupling agent is from 0.06 to 0.50%,preferably 0.10 to 0.35% in terms of its adhered amount on the glassfiber.

In the surface treatment, the silane coupling agent is usually used inthe form of an aqueous solution, but it can also be used in the form ofa mixed solution of water and an organic solvent such as an alcohol, aketone or a glycol ether.

In that case, a pH of the solution containing the silane coupling agentis 4 or less, preferably in the range of from 2 to 4. As the organicsolvent, methanol is particularly preferable, and the concentration ofthe silane coupling agent in the solution is preferably from 30 to 40%.The other steps for the surface treatment of the glass fiber can becarried out in a usual manner. That is, an application step is done byan immersion step or the use of a roll coater or by means of spraying orthe like at ordinary temperature.

As the glass fiber, E glass (non-alkali fiber glass for electric uses)is particularly preferable, but S glass (high-strength glass), D glass(low-dielectric glass) and quartz glass can be also utilized.Furthermore, examples of the glass fiber product include glass cloth,glass tape, glass yarn, glass roving, glass mat, glass paper and glasspowder.

The silane coupling agent of the present invention is excellent inaffinity for and compatibility with thermosetting resins andthermoplastic resins. Therefore, when the surface of the glass fiberproduct is treated with the silane coupling agent, the affinity, i.e.adhesion between the glass fiber product and the above-mentoned matrixresin can be improved.

This reason would be as follows: A general conventional silane couplingagent contains, as the main component, a compound having one silyl group[--Si(OR)₃ ] in its molecule, but the silane coupling agent of thepresent invention contains, as the fundamental component, the reactionproduct obtained by reacting each diamine with the haloalkylalkoxysilanein a specific molar ratio. That is, the silane coupling agent of thepresent invention is basically, for example, a silane coupling agentprepared by reacting 2.3 to 4.0 mols of a haloalkylalkoxysilane with 1mol of a diamine having N atoms to which 4 active hydrogen atoms arebound, a silane coupling agent prepared by reacting 1.3 to 3.0 mols of ahaloalkylalkoxysilane with 1 mol of a diamine having N atoms to one ofwhich one alkylsilyl group is bound and to the residual bonds of which 3active hydrogen atoms are bound or a silane coupling agent prepared byreacting 0.3 to 2.0 mols of a haloalkylalkoxysilane with1 mol of adiamine having N atoms to each or either of which 2 alkylsilyl groupsare bound and to each or either of which 2 active hydrogen atoms arebound.

Therefore, the silane coupling agent of the present invention contains,as the main components, the reaction product having 2 silyl groups, thereaction product having 3 silyl groups and the reaction product havingthe 4 silyl groups, and if the silane coupling agent of the presentinvention is regarded as a mixture of these reaction products, 2.3 ormore silyl groups are contained in one molecule of the agent.

With regard to the silane coupling agent of the present invention, when--Si(OR)₃ is hydrolyzed to --Si(OH)₃, the group which reacts with thesilanol group on the surface of the glass fiber is present 2.3 times ormore as much as in the conventional silane coupling agent. Additionally,when a siloxane bond is formed, a crosslinking density in the molecularstructure of the siloxane is heightened 2.3-fold or more by the reactivegroup which is present 2.3 times or more than in the conventional one,so that a closer network structure is formed. In consequence, waterresistance and adhesive strength increase, and heat resistance alsoimproves.

If the molar ratio between the diamine and the haloalkylalkoxysilane islower than the above-mentioned range, for example, if the molar ratio ofthe haloalkylalkoxysilane to the diamine having N atoms to which 4active hydrogen atoms are bound is less than 2.3, a sufficient effectcannot be obtained. This fact indicates that when the number of thesilyl groups present in one molecule of the diamine is 2 on the average,the closer network structure can scarcely be obtained.

Also, when the haloalkylalkoxysilane which reacts with the diamine is acompound having the formula ##STR2## wherein each of R¹ and R² areindependently a substituted or unsubstituted alkyl group an aryl groupor an alkenyl group each having 1 to 6 carbon atoms, R³ is astraight-chain or branched alkylene group having 1 to 6 carbon atoms, nis 1, 2 or 3, and X is a halogen atom,

a similar effect can he obtained as compared with the case where thesilyl group is -Si(OR)3.

The forth silane coupling agent of the present invention to which thehalomethylstyrene is added has a styryl group in its molecule, andtherefore this type of silane coupling agent has increased affinity forand compatibility with a matrix resin. In consequence, a greater effectcan be expected.

The silane coupling agent of the present invention is a mixture of thereaction products in which isomers and homologues are present, andtherefore the constitutional ratio of the products can be adjusted byoptimizing the blend ratio of the raw materials and reaction conditionsso as to adapt changes in preparation conditions of a treating agent,treatment conditions and the like at the time when the product is usedas a surface treating agent.

An inorganic material treated by the silane coupling agent of thepresent invention can be mixed with a thermosetting resin such as epoxyresin or polyimide resin and then thermally cured, thereby obtaining astrong composite material.

In particular, a glass fiber base material treated with the silanecoupling agent of the present invention can have excellent affinity forand compatibility with a matrix resin as well as improved adhesion tothe matrix resin. Therefore, printed-circuit boards manufactured byusing the glass fiber base material of the present invention areexcellent in heat resistance such as soldering heat resistance or heatshock resistance, water absorption properties and solvent resistance.

EXAMPLES

Now, the present invention will be described in detail with reference toexamples, but the scope of the present case should not be limited tothese examples.

In the examples and comparative examples, mols of each component in amixture are expressed in terms of an average composition.

Example 1

In a 10-liter flask, the inner atmosphere of which was previouslyreplaced with dried nitrogen, were placed 1,606 g (7.23 mols) ofN-2-aminoethylaminopropyltrimethoxysilane, 2,440 g (12.3 mols) of3-chloropropyltrimethoxysilane and xylene, and reaction was thenperformed with stirring at 130° C. for 5 hours. Next, 1,630 g of asodium methylate solution (28% methanol solvent; in the following, thissolvent was similarly used) was added dropwise thereto over about 4hours. Afterward, the reaction was further continued for 5 hours, and740 g of the sodium methylate solution was then added dropwise theretoagain over 2 hours to perform the reaction. During this operationvaporized methanol was distilled off in order to maintain the desiredreaction temperature.

After completion of the reaction, secondarily produced sodium chloridewas removed from the system, whereby a light brown reaction solution wasobtained.

This reaction solution was then analyzed by gas chromatography, and itwas confirmed that the raw materials were consumed. According to silvernitrate titration, it was found that the amount of chlorine present was240 ppm, which means that most of the sodium chloride by-product wasremoved therefrom.

Furthermore, methanol and xylene were removed from this reactionsolution in order to obtain a reaction product. The latter was thenanalyzed by NMR, and it was confirmed that the product had the followingstructure.

Results of NMR analysis:

    ______________________________________                                                               Intensity Ratio                                                           (ppm) Found   Calcd.                                       ______________________________________                                         ##STR3##            0.6     2.0 H   2.0 H                                     ##STR4##            1.5     2.7 H   2.5 H                                     ##STR5##            2.4     3.8 H   3.5 H                                     ##STR6##            3.5     8.5 H   9.0 H                                    ______________________________________                                    

Structural formula: ##STR7## wherein m+n=2.7.

Example 2

In a 10-liter flask, the inner atmosphere of which was previouslyreplaced with dried nitrogen, were placed 1,700 g (8.25 mols) ofN-2-aminoethylaminopropylmethyldimethoxysilane, 2,110 g (11.5 mols) of3-chloropropylmethyldimethoxysilane and xylene, and reaction was thenperformed with stirring at 130° C. for 5 hours. Next, 1,560 g of asodium methylate solution was added dropwise thereto over about 4 hours.Afterward, the reaction was further continued for 5 hours, and 667 g ofthe sodium methylate solution was then added dropwise thereto again over2 hours to perform the reaction. During this operation, vaporizedmethanol was distilled off in order to maintain the desired reactiontemperature.

After completion of the reaction, secondarily produced sodium chloridewas removed from the system, whereby a light brown reaction solution wasobtained.

This reaction solution was then analyzed by gas chromatography, and itwas confirmed that the raw materials were consumed. According to silvernitrate titration, it was found that the amount of chlorine present was210 ppm, which means that most of the sodium chloride by-product wasremoved therefrom.

Furthermore, methanol and xylene were removed from this reactionsolution in order to obtain a reaction product. The latter was thenanalyzed by NMR, and it was confirmed that the product had the followingstructure.

Results of NMR analysis:

    ______________________________________                                                               Intensity Ratio                                                           (ppm) Found   Calcd.                                       ______________________________________                                         ##STR8##            0.1     2.9 H   3.0 H                                     ##STR9##            0.6     2.0 H   2.0 H                                     ##STR10##           1.5     2.8 H   2.7 H                                     ##STR11##           2.4     3.6 H   3.7 H                                     ##STR12##           3.5     5.7 H   6.0 H                                    ______________________________________                                    

Structural formula: ##STR13## wherein m+n=2.4

Examples 3 and 4, Comparative Example 1

The same procedure as in Example 1 was repeated with the exception thatamounts of the raw materials were changed as shown in Table 1, in orderto obtain reaction products.

With regard to these reaction products, analyzed values of chlorinepresent by silver nitrate titration and proton ratios measured by NMRanalysis are set forth in Tables 2 and 3, respectively. Moreover, astructural formula is also shown hereinafter.

                  TABLE 1                                                         ______________________________________                                        Raw Material  Example 3 Example 4 Comp. Ex. 1                                 ______________________________________                                        3-Chloropropyltri-                                                                          2,440 g   2,440 g   2,440 g                                     methoxysilane (12.3)    (12.3)    (12.3)                                      N-2-Aminoethylamino-                                                                        1,950 g   1,365 g   2,730 g                                     propyltrimethoxysilane                                                                       (8.8)    (6.15)    (12.3)                                      ______________________________________                                         Note:                                                                         The value in each pair of parentheses denotes mols.                      

                  TABLE 2                                                         ______________________________________                                                   Example 3                                                                              Example 4 Comp. Ex. 1                                     ______________________________________                                        Content of Cl (ppm)                                                                        400        570       410                                         ______________________________________                                    

Structural formula ##STR14## wherein in the reaction product of Example3, m+n=2.4, in the reaction product of Example 4, m+n=3.0, and in thereaction product of Comparative Example 1, m+n=2.0.

                                      TABLE 3                                     __________________________________________________________________________    (Intensity Ratio)                                                                                     Reaction Product                                                                       Reaction Product                                                                       Reaction Product                                            in Example 3                                                                           in Example 4                                                                           Comp. Example 1                                         (ppm)                                                                             Found                                                                             Calcd.                                                                             Found                                                                             Calcd.                                                                             Found                                                                             Calcd.                          __________________________________________________________________________     ##STR15##          0.6 2.1 H                                                                             2.0 H                                                                              2.0 H                                                                             2.0 H                                                                              2.0 H                                                                             2.0 H                            ##STR16##          1.5 2.6 H                                                                             2.7 H                                                                              2.5 H                                                                             2.3 H                                                                              3.1 H                                                                             3.0 H                            ##STR17##          2.4 3.9 H                                                                             3.7 H                                                                              3.4 H                                                                             3.3 H                                                                              4.1 H                                                                             4.0 H                            ##STR18##          3.5 8.9 H                                                                             9.0 H                                                                              8.7 H                                                                             9.0 H                                                                              8.8 H                                                                             9.0 H                           __________________________________________________________________________

Example 5

In a 10-liter flask, the inner atmosphere of which was previouslyreplaced with dried nitrogen, was placed 2,270 g (37.8 mols) ofethylenediamine, and 3,000 g (15.1 mols) of3-chloropropyltrimethoxysilane was added thereto dropwise with stirringover 1 hour, while temperature was maintained at 85° C., and reactionwas further carried out for 4 hours. The resulting reaction solution wasanalyzed by gas chromatography, and it was confirmed that the rawmaterials were consumed.

After stirring was stopped, the reaction solution was cooled to 50° C.,so that it was separated into 2 layers. The upper layer was taken outtherefrom and then subjected to quantitative analysis by silver nitratetitration, and it was confirmed that the content of chlorine present was1,700 ppm, which means that the chlorine atom derived from3-chloropropyltrimethoxysilane was scarcely present in the upper layer.Furthermore, this upper layer (hereinafter referred to as "reactionproduct H") was analyzed by NMR, and it was also confirmed that thereaction product H had the following structure.

Structural formula: ##STR19## wherein m+n=1.1.

Results of NMR analysis:

    ______________________________________                                                               Intensity Ratio                                                           (ppm) Found   Calcd.                                       ______________________________________                                         ##STR20##           0.6     1.8 H   2.0 H                                     ##STR21##           1.5     4.6 H   4.6 H                                     ##STR22##           2.4     5.6 H   5.6 H                                     ##STR23##           3.5     9.0 H   9.0 H                                    ______________________________________                                    

Furthermore, in a 5-liter flask, the inner atmosphere of which waspreviously replaced with dried nitrogen, were placed 500 g (2.10 moles)of this reaction product H, 708 g (3.57 mols) of3-chloropropyltrimethoxysilane and xylene, and reaction was thenperformed with stirring at 135° C. for 5 hours. Next, 480 g of a sodiummethylate solution was added dropwise thereto over about 2 hours.Afterward, the reaction was further continued for 5 hours, and 207 g ofthe sodium methylate solution was then added dropwise thereto again over1 hour to perform the reaction. During this operation, vaporizedmethanol was distilled off in order to maintain the desired reactiontemperature.

After completion of the reaction, secondarily produced sodium chloridewas removed from the system, whereby a light brown reaction solution wasobtained.

This reaction solution was then analyzed by gas chromatography, and itwas confirmed that the raw materials were consumed. According to silvernitrate titration, it was found that the amount of chlorine present was570 ppm, which means that most of the sodium chloride by-product wasremoved therefrom.

Furthermore, methanol and xylene were removed from this reactionsolution in order to obtain a reaction product. The latter was thenanalyzed by NMR, and it was confirmed that the product had the followingstructure.

Structural formula: ##STR24## wherein m+n=2.8.

Results of NMR analysis:

    ______________________________________                                                               Intensity Ratio                                                           (ppm) Found   Calcd.                                       ______________________________________                                         ##STR25##           0.6     2.1 H   2.0 H                                     ##STR26##           1.5     2.3 H   2.4 H                                     ##STR27##           2.4     3.5 H   3.4 H                                     ##STR28##           3.5     8.9 H   9.0 H                                    ______________________________________                                    

Comparative Example 2

In a 5-liter flask, the inner atmosphere of which was previouslyreplaced with dried nitrogen, were placed 500 g (2.10 mols) of thereaction product H obtained in Example 5, 167 g (0.84 mole) of3-chloropropyltrimethoxysilane and xylene, and reaction was thenperformed with stirring at 135° C. for 5 hours. Next, 115 g of a sodiummethylate solution was added dropwise thereto over about 2 hours.Afterward, the reaction was further continued for 5 hours, and 47 g ofthe sodium methylate solution was then added dropwise thereto again over1 hour to perform the reaction. During this operation, vaporized methodwas distilled off in order to maintain the desired reaction temperature.

After completion of the reaction, secondarily produced sodium chloridewas removed from the system, whereby a light brown reaction solution wasobtained.

This reaction solution was then analyzed by gas chromatography, and itwas confirmed that 3-chloropropyltrimethoxysilane was consumed.According to silver nitrate titration, it was found that the amount ofchlorine present was 470 ppm, which meant that most of the sodiumchloride by-product was removed therefrom.

Moreover, methanol and xylene were removed from this reaction solutionin order to obtain a reaction product. The latter was then analyzed byNMR, and it was confirmed that the product had the following structure.

Structural formula: ##STR29## wherein m+n=1.5.

Results of NMR analysis:

    ______________________________________                                                               Intensity Ratio                                                           (ppm) Found   Calcd.                                       ______________________________________                                         ##STR30##           0.6     2.2 H   2.0 H                                     ##STR31##           1.5     3.7 H   3.7 H                                     ##STR32##           2.4     4.8 H   4.7 H                                     ##STR33##           3.5     8.8 H   9.0 H                                    ______________________________________                                    

Example 6

In a 10-liter flask, the inner atmosphere of which was previouslyreplaced with dried nitrogen, were placed 2,322 g (6.05 mols) ofN,N'-bis(trimethoxysilylpropyl)ethylenediamine, 600 g (3.02 mols) of3-chloropropyltrimethoxysilane and xylene, and reaction was thenperformed with stirring at 130° C. for 5 hours. Next, 408 g of a sodiummethylate solution was added dropwise thereto over about 1 hour.Afterward, the reaction was further continued for 4 hours, and 175 g ofthe sodium methylate solution was then added dropwise thereto again over1 hour to perform the reaction. During this operation, vaporizedmethanol was distilled off in order to maintain the desired reactiontemperature.

After completion of the reaction, secondarily produced sodium chloridewas removed from the system, whereby a light brown reaction solution wasobtained.

This reaction solution was then subjected to silver nitrate titration,and it was found that the amount of chlorine present was 370 ppm, whichmeant that most of the sodium chloride by-product was removed therefrom.

Furthermore, methanol and xylene were removed from this reactionsolution in order to obtain a reaction product. The latter was thenanalyzed by NMR, and it was confirmed that the product had the followingstructure.

Results of NMR analysis:

    ______________________________________                                                               Intensity Ratio                                                           (ppm) Found   Calcd.                                       ______________________________________                                         ##STR34##           0.6     2.0 H   2.0 H                                     ##STR35##           1.5     2.5 H   2.6 H                                     ##STR36##           2.4     3.7 H   3.6 H                                     ##STR37##           3.5     8.6 H   9.0 H                                    ______________________________________                                    

Structural formula: ##STR38## wherein m+n=2.5.

Example 7

In a 10-liter flask, the inner atmosphere of which was previouslyreplaced with dried nitrogen, were placed 2,250 g (4.52 mols) of themethanol-free and xylene-free reaction product (reaction product F)obtained in Example 1 and 2,250 g of methanol, and while the resultingmixture was maintained at 50° C., a mixed solution of 690 g (4.52 mols)of chloromethylstyrene and 690 g of methanol were added dropwise theretoover 4 hours.

Afterward, the reaction was performed at the same temperature for 10hours. After completion of the reaction, the resulting reaction productwas analyzed by gas chromatography, and it was confirmed that the rawmaterials were consumed.

Moreover, this reaction solution was then subjected to silver nitratetitration, and it was found that 98% or more of chlorine derived fromchloromethylstyrene was converted into hydrochloric acid.

Examples 8, 9 and 10

The same procedure as in Example 7 was repeated with the exception thateach ratio of materials was changed as shown in Table 4, in order toobtain reaction products.

Each reaction product was then analyzed by gas chromatography, and itwas confirmed that most of the raw materials were consumed.

Moreover, each reaction solution was then subjected to silver nitratetitration, it was found that 98% or more of a chlorine atom derived fromchloromethylstyrene was converted into hydrochloric acid.

                  TABLE 4                                                         ______________________________________                                        Material      Example 8 Example 9  Example 10                                 ______________________________________                                        Reaction Product F                                                                          2,400 g   2,400 g    --                                         in Example 1  (4.82)    (4.82)     --                                         Reaction Product F                                                                          --        --         2,400 g                                    in Example 2  --        --         (5.83)                                     Methanol      2,400 g   2,400 g    2,400 g                                    (for dissolving                                                                             --        --         --                                         reaction product F)                                                           Chloromethylstyrene                                                                           660 g     150 g      403 g                                                  (4.33)    (0.98)     (2.64)                                     Methanol        660 g     150 g      403 g                                    (for dissolving                                                                             --        --         --                                         chloromethylstyrene)                                                          Molar Ratio (%) of                                                                          69.1      15.6       28.3                                       Chloromethylstyrene                                                           to Remaining Active                                                           Hydrogen of Reaction                                                          Product F                                                                     ______________________________________                                         Note:                                                                         The value in each pair of parentheses denotes mol or mols.               

Example 11

Pieces of glass cloth were treated with the silane coupling agentsobtained in Examples 1 to 10 and the reaction products obtained inComparative Examples 1 and 2, and epoxy prepregs were made of thetreated pieces of glass cloth. Afterward, epoxy laminates were preparedfrom the epoxy prepregs.

Comparative Examples 3, 4 and 5)

For comparison, epoxy resin laminates were prepared in like manner,using γ-glycidoxypropyltrimethoxysilane (trade name S510 made by ChissoCorp.), 3-(N-styrylmethyl-2-aminoethyl

amino)propyltrimethoxysilane hydrochloride andN,N'-bis-(trimethoxysilylpropyl)ethylenediamine. They are-respectivelyComparative Examples 3,4 and 5.

Afterward, the respective epoxy resin laminates were evaluated, and theresults are set forth in Table 5.

In the present invention, performances of the products were evaluated asfollows:

Treatment of Glass Cloth

Each of the reaction products obtained in Examples 1, 2, 3, 4, 5 and 6as well as Comparative Examples 1 and 2 was dissolved in methanol toprepare a solution having a solids content of 50%. Furthermore, thecompositions obtained in Examples 7 to 10,γ-glycidoxypropyltrimethoxysilane andN,N'-bis(trimethoxysilylpropyl)ethylenediamine were used directlywithout any treatment. The compound3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxysilane hydrochloridewas used in the form of a methanol solution having a solids content was40%.

The above-mentioned silane coupling agent was dissolved in distilledwater, the pH of which was previously adjusted to 4 with acetic acid, inorder to prepare a solution having a solids content of 0.5% by weight.Each of γ-glycidoxypropyltrimethoxysilane andN,N'-bis(trimethoxysilylpropyl)ethylenediamine was dissolved indistilled water, the pH of which was previously adjusted to 4 withacetic acid, in order to prepare a solution having a solids content was0.5% by weight. Moreover,3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxysilane hydrochloridewas dissolved in distilled water, the pH of which was previouslyadjusted to 2.5 with formic acid, in order to prepare a solution havinga solids content of 0.5% by weight.

Each piece of heat cleaned glass cloth (glass fiber fabric made by NittoBoseki Co., Ltd.; trade name WEA-18K) was immersed in each of theabove-mentioned solutions and then squeezed by squeeze rolls, followedby drying at 110° C. for 10 minutes.

Preparation of Laminate Specimens

Pieces of surface-treated glass cloth were impregnated with G-10 typeepoxy resin (trade name Epicoat 1001 made by Shell Petrochemical Co.,Ltd.) and then dried at 130° C. for 15 minutes in order to formprepregs. Eight sheets of these prepregs were superposed upon eachother, and these prepregs were then sandwiched between two copper foils.Afterward, the sandwiched prepregs were heated at 175° C. for 60 minutesunder a load of 30 kg/cm² so as to perform molding. The copper foilswere then removed therefrom by etching, thereby preparing specimens.

(1) Boiling Water Ahsorption Rate

In accordance with a test procedure of JIS C-6481, each laminatespecimen, was boiled for a period of 5 to 20 hours, and afterward thewater absorption rate was measured.

(2) Soldering Heat Resistance Test

Each laminate specimen was boiled in a pressure cooker at 133° C. andthen immersed in a solder bath at 280° C. for 20 seconds. After thespecimen was taken out therefrom, blister or peeling on the specimenwere observed. The boiling time until the occurrence of these drawbackswas regarded as the soldering heat resistance time.

(3) Heat Shock Resistance

Each laminate specimen was immersed in liquid nitrogen for about 1minute, and immediately it was then floated on a solder bath at 280° C.Afterward, damage to the specimen was observed, and evaluation was madeon the basis of the following standards.

○. . . No. damage was observed.

∘. . . Spot-like damage occurred slightly.

Δ. . . A great deal of spot-like damage occurred.

X . . . Spot-like damage occurred all over the surface.

(4) Resin Impregnation Characteristics (prepreg) Resin impregnationstates were observed, and evaluation was made on the basis of thefollowing standards.

⊚. . . Transparency was very good.

∘. . . Transparency was good.

Δ. . . Transparency was slightly bad.

X . . . Transparency was bad.

(5) Methylene Chloride Resistance

In accordance with JIS C-6481, each laminate specimen was immersed inmethylene chloride at 20° C. for 1 hour, and evaluation was then made byobserving the appearance of the specimen.

                                      TABLE 5                                     __________________________________________________________________________           Content                         Impreg-                                       (%) of                                                                             Water Absorption Rate (%)                                                                   Solder Heat  nation                                                                             Methylene                                Resin in                                                                           at Each Boiling Time                                                                        Resistance                                                                           Heat Shock                                                                          of Resin                                                                           Chloride                                 Laminate                                                                           5 h. 10 h.                                                                             20 h.                                                                              Time (min)                                                                           Resistance                                                                          (prepreg)                                                                          Resistance                        __________________________________________________________________________    Example 1                                                                            41.2 0.52 0.63                                                                              0.84 120    ⊚                                                                    ◯                                                                      not                                                                           changed                           Example 2                                                                            41.2 0.51 0.63                                                                              0.81 120    ⊚                                                                    ◯                                                                      not                                                                           changed                           Example 3                                                                            40.8 0.52 0.64                                                                              0.84 115    ⊚                                                                    ◯                                                                      not                                                                           changed                           Example 4                                                                            40.5 0.51 0.63                                                                              0.83 115    ⊚                                                                    ◯                                                                      not                                                                           changed                           Example 5                                                                            40.9 0.52 0.61                                                                              0.81 120    ⊚                                                                    ◯                                                                      not                                                                           changed                           Example 6                                                                            41.0 0.51 0.62                                                                              0.82 115    ⊚                                                                    ◯                                                                      not                                                                           changed                           Example 7                                                                            40.8 0.51 0.61                                                                              0.81 120    ⊚                                                                    ⊚                                                                   not                                                                           changed                           Example 8                                                                            41.0 0.50 0.60                                                                              0.80 120    ⊚                                                                    ⊚                                                                   not                                                                           changed                           Example 9                                                                            40.4 0.51 0.61                                                                              0.81 120    ⊚                                                                    ⊚                                                                   not                                                                           changed                           Example 10                                                                           40.8 0.52 0.61                                                                              0.83 120    ⊚                                                                    ⊚                                                                   not                                                                           changed                           Comparative                                                                          40.7 0.62 0.67                                                                              0.93 100    Δ                                                                             ◯                                                                      slightly                          Example 1                                   changed                           Comparative                                                                          40.9 0.60 0.71                                                                              0.91 100    Δ                                                                             ◯                                                                      slightly                          Example 2                                   changed                           Comparative                                                                          40.9 0.67 0.73                                                                              1.02  75    X     Δ                                                                            a little                          Example 3                                   changed                           Comparative                                                                          41.3 0.63 0.71                                                                              1.01 105    Δ                                                                             ⊚                                                                   slightly                          Example 4                                   changed                           Comparative                                                                          41.1 0.62 0.68                                                                              0.92 100    Δ                                                                             ◯                                                                      slightly                          Example 5                                   changed                           __________________________________________________________________________

As shown in Table 5, the products prepared in the respective examplesaccording to the present invention have much better results than theproducts prepared in the respective comparative examples, particularly3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxysilane hydrochloridewhich is presently often used as a silane coupling agent forprinted-circuit boards, in all points of water absorption, solderingheat resistance, heat shock resistance and methylene chlorideresistance.

What is claimed is:
 1. A glass fiber product for laminates comprising aglass fiber material treated with a silane coupling agent prepared byreacting 2.3 to 4.0 mols of a haloalkylalkoxysilane with 1 mole of adiamine having N atoms to which 4 active hydrogen atoms are bound.
 2. Aglass fiber product for laminates comprising a glass fiber materialtreated with a silane coupling agent prepared by reacting 1.3 to 3.0mols of a haloalkylalkoxysilane with 1 mol of a diamine having N atomsto one of which one alkylsilyl group is bound and to the residual bondsof which 3 active hydrogen atoms are bound.
 3. A glass fiber product forlaminates comprising a glass fiber material treated with a silanecoupling agent prepared by reacting 0.3 to 2.0 mols of ahaloalkylalkoxysilane with 1 mol of a diamine having N atoms to each oreither of which 2 alkylsilyl groups are bound and to each or either ofwhich 2 active hydrogen atoms are bound.
 4. A glass fiber product forlaminates comprising a glass fiber material treated with a silanecoupling agent prepared by reacting a halomethylstyrene with (a) areaction product obtained by reacting 2.3 to 3.5 mols of ahaloalkylalkoxysilane with 1 mol of a diamine having N atoms to which 4active hydrogen atoms are bound, (b) a reaction product obtained byreacting 1.3 to 2.5 mols of a haloalkylalkoxysilane with 1 mol of adiamine having N atoms to one of which one alkylsilyl group is bound andto the residual bonds of which 3 active atoms are bound or (c) areaction product obtained by reacting 0.3 to 1.5 mols of ahaloalkylalkoxysilane with 1mol of a diamine having N atoms to each oreither of which 2 active hydrogen atoms are bound and to each or eitherof which 2 alkylsilyl groups are bound, the amount of saidhalomethylstyrene being not more than 80 mol% of mol amounts given bysubtracting the mols of said haloalkylalkoxysilane used from the mols ofsaid active hydrogen atoms of said diamine used.
 5. A glass fiberproduct for laminates comprising a glass fiber material treated with asilane coupling agent according to claim 4 wherein saidhalomethylstyrene is chloromethylstyrene.
 6. A glass fiber product forlaminates comprising a glass fiber material treated with a silanecoupling agent according to claim 1 wherein said haloalkylalkoxysilaneis a compound represented by the formula ##STR39## wherein each of R¹and R² are independently a substituted or unsubstituted alkyl group, anaryl group or an alkenyl group having 1 to 6 carbon atoms, R³ is astraight-chain or branched alkylene group having 1 to 6 carbon atoms, nis 1, 2 or 3, and X is a halogen atom.
 7. A glass fiber product forlaminates comprising a glass fiber material treated with a silanecoupling agent according to claim 2 wherein said haloalkylalkoxysilaneis a compound represented by the formula ##STR40## wherein each of R¹and R² are independently a substituted or unsubstituted alkyl group, anaryl group or an alkenyl group having 1 to 6 carbon atoms, R³ is astraight-chain or branched alkylene group having 1 to 6 carbon atoms, nis 1, 2 or 3, and X is a halogen atom.
 8. A glass fiber product forlaminates comprising a glass fiber material treated with a silanecoupling agent according to claim 3 wherein said haloalkylalkoxysilaneis a compound represented by the formula ##STR41## wherein each of R¹and R² are independently a substituted or unsubstituted alkyl group, anaryl group or an alkenyl group having 1 to 6 carbon atoms, R³ is astraight-chain or branched alkylene group having 1 to 6 carbon atoms, nis 1, 2 or 3, and X is a halogen atoms.
 9. A glass fiber product forlaminates comprising a glass fiber material treated with a silanecoupling agent according to claim 4 wherein said haloalkylalkoxysilaneis a compound represented by the formula ##STR42## wherein each of R¹and R² are independently a substituted or unsubstituted alkyl group, anaryl group or an alkenyl group having 1 to 6 carbon atoms, R³ is astraight-chain or branched alkylene group having 1 to 6 carbon atoms, nis 1, 2 or 3, and X is a halogen atom.
 10. A glass fiber product forlaminates comprising a glass fiber material treated with a silanecoupling agent according to claim 5 wherein said haloalkylalkoxysilaneis a compound represented by the formula ##STR43## wherein each of R¹and R² are independently a substituted or unsubstituted alkyl group, anaryl group or an alkenyl group having b 1 to 6 carbon atoms, R³ is astraight-chain or branched alkylene group having 1 to 6 carbon atoms, nis 1, 2 or 3, and X is a halogen atom.
 11. A glass fiber product forlaminates according to claim 1 wherein said silane coupling agentincludes at least two silyl groups per molecule.
 12. A glass fiberproduct for laminates according to claim 2 wherein said silane couplingagent includes at least two silyl groups per molecule.
 13. A glass fiberproduct for laminates according to claim 3 wherein said silane couplingagent includes at least two silyl groups per molecule.
 14. A glass fiberproduct for laminates according to claim 4 wherein said silane couplingagent includes at least two silyl groups per molecule.
 15. A glass fiberproduct for laminates according to claim 4 wherein said silane couplingagent comprises the product of a reaction between a halomethylstyrenewith the reaction product obtained from the reaction of 2.3 to 3.5 molsof a haloalkylalkoxysilane with 1 mole of a diamine having N atoms, towhich four active hydrogen atoms are bound.
 16. A glass fiber productfor laminates according to claim 4 wherein said silane coupling agentcomprises the reaction product of a halomethylstyrene with the reactionproduct obtained from the reaction of 1.3 to 2.5 mols of ahaloalkylalkoxysilane with 1 mol of a diamine having N atoms, to one ofwhich one alkylsilyl group is bound and to the residual bonds of whichthree active hydrogen atoms are bound.
 17. A glass fiber product forlaminates according to claim 4 wherein said silane coupling agentcomprises the reaction product of a halomethylstyrene with the reactionproduct obtained from the reaction of 0.3 to 1.5 mols of a haloalkyl-alkoxysilane with 1 mol of a diamine having N atoms, to each or eitherof which two active hydrogen atoms are bound and to each or other ofwhich two alkylsilyl groups are bound.